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United States Patent |
5,545,694
|
Satake
,   et al.
|
August 13, 1996
|
Reactive microgel and photosensitive resin composition containing the
reactive microgel for flexographic printing plate
Abstract
A reactive microgel suitable for a photosensitive resin composition for a
water-developable flexographic printing plate, which has an average
particle diameter of 1 to 10 .mu.m, and is formed of
microgel particles, as a core, synthesized from an acrylic monomer in an
aqueous medium in the presence of an oil-soluble initiator and in the
presence of a reactive polymer emulsifier which is an adduct of a
neutralized product of an acrylic copolymer having a tertiary amino group
with a compound having an epoxy group and an .alpha.,.beta.-unsaturated
double bond, and a nonionic emulsifier having an HLB of 12 to 16, and
a compound having an epoxy group and an .alpha.,.beta.-unsaturated double
bond, attached to surfaces of the microgel particles.
Inventors:
|
Satake; Sunao (Tokyo, JP);
Yatsuyanagi; Yoshimi (Tokyo, JP);
Fujii; Masahiro (Tokyo, JP);
Imagawa; Ippei (Tokyo, JP)
|
Assignee:
|
Toyo Ink Manufacturing Co., Ltd. (Tokyo, JP)
|
Appl. No.:
|
386087 |
Filed:
|
February 9, 1995 |
Foreign Application Priority Data
Current U.S. Class: |
525/286 |
Intern'l Class: |
C08F 269/00 |
Field of Search: |
525/286
|
References Cited
U.S. Patent Documents
5120796 | Jun., 1992 | Fukuchi | 525/286.
|
Foreign Patent Documents |
0556403 | Aug., 1993 | EP.
| |
Other References
Patent Abstracts of Japan; JP5032743, Feb. 9, 1993; abstract.
|
Primary Examiner: Lipman; Bernard
Attorney, Agent or Firm: Wenderoth, Lind & Ponack
Claims
What is claimed is:
1. A reactive microgel having an average particle diameter of 1 to 10
.mu.m, formed of
microgel particles, as a core, synthesized from an acrylic monomer in an
aqueous medium in the presence of an oil-soluble initiator and in the
presence of a reactive polymer emulsifier which is an adduct of a
neutralized product of an acrylic copolymer having a tertiary amino group
with a compound having an epoxy group and an .alpha.,.beta.-unsaturated
double bond, and a nonionic emulsifier having an HLB of 12 to 16, and
a compound having an epoxy group and an .alpha.,.beta.-unsaturated double
bond, attached to surfaces of the microgel particles.
2. A reactive microgel according to claim 1, wherein the acrylic copolymer
having a tertiary amino group is a copolymer obtained by polymerizing an
acrylic monomer having a tertiary amino group and other acrylic monomer.
3. A reactive microgel according to claim 2, wherein the acrylic copolymer
having a tertiary amino group contains 10 to 50% by weight of a component
from the acrylic monomer having a tertiary amino group.
4. A reactive microgel according to claim 1, wherein the acrylic copolymer
having a tertiary amino group has a glass transition temperature of
20.degree. C. or lower.
5. A reactive microgel according to claim 1, wherein the microgel particles
are microgel particles synthesized in the presence of the reactive polymer
emulsifier in an amount of 1 to 20 parts by weight per 100 parts by weight
of the acrylic monomer to form the core.
6. A reactive microgel according to claim 1, wherein the microgel particles
are microgel particles synthesized in the presence of the nonionic
emulsifier in an amount of 0.1 to 15 parts by weight per 100 parts by
weight of the acrylic monomer to form the core.
7. A reactive microgel according to claim 1, wherein the microgel particles
are microgel particles synthesized in the presence of the oil-soluble
initiator in an amount of 0.1 to 5 parts by weight per 100 parts by weight
of the acrylic monomer to form the core.
8. A reactive microgel according to claim 1, wherein the microgel particles
are microgel particles synthesized from the acrylic monomer containing 1
to 40% by weight of a polyfunctional acrylic monomer.
9. A reactive microgel according to claim 1, wherein the reactive microgel
has a refractive index of 1.46 to 1.49.
Description
FIELD OF THE INVENTION
The present invention relates to a novel reactive microgel and a
photosensitive resin composition for a water-developable flexographic
printing plate. More specifically it relates to a reactive microgel having
water-developability useful as a raw material for a water-developable
flexographic printing plate, and a photosensitive resin composition
containing the reactive microgel used for a water-developable flexographic
printing plate.
PRIOR ART OF THE INVENTION
In recent years, flexographic printing has been spotlighted with the
modernization of packaging. The method of producing a conventional
flexographic printing plate requires at least three steps of the
preparation of a printing plate of a metal, the replication and the
vulcanization of a rubber, and these steps require technical proficiency
and a long period of time for the production. That is, the conventional
flexographic printing plate has been expensive. For overcoming this
defect, a solvent-developable printing plate of a photosensitive resin has
been developed so that a flexographic printing plate can be produced in a
simple process. For the solvent-developable printing plate, however, it is
required to use a halogen-containing solvents such as trichloroethylene or
perchloroethylene as a developer solution. The solvent-developable
printing plate therefore tends to be limited in use in view of recent
problems of an adverse influence on the environment and harmfulness to a
human body.
On the other hand, studies have been made of halogen-free substitute
solvents as a developer solution. However, these substitute solvents are
limited in use since they are insufficient in development and combustible.
Further, for a solvent-developable flexographic printing plate, a
diene-based rubber material having a high molecular weight is used as a
raw material in many cases, and the solvent-developable flexographic
printing plate structurally has problems in that it is poor in heat
resistance, oxidation resistance and ozone resistance. It has been
therefore desired to develop a water-developable flexographic printing
plate which is harmless to a human body and is free from causing
environmental problems.
Under the circumstances, JP-A-60-173055 and JP-A60-211451 discloses
compositions containing a hydrophobic elastomeric material and a
hydrophilic polymer compound. However, these compositions have a defect in
that the flexographic printing plates obtained therefrom are poor in water
resistance, since the compositions contain a relatively large amount of
the hydrophilic polymer compound for achieving sufficient developability
with water.
On the other hand, JP-A-62-173455 and JP-A-63-8648 disclose a
photosensitive material containing fine particles of a resin or a
microgel, or a composition for a flexographic printing plate. However, it
is not sufficient for obtaining developability with water to simply
contain the fine particles of a resin or a microgel. Further, this
composition in which the fine particles of a resin are dispersed in a
matrix having a high molecular weight is an inherently nonhomogeneous
system, and a flexographic printing plate made of the composition is
non-transparent due to the refractive index difference of the composition.
As a result, no sufficient resolution can be accomplished. Further, when
attempts are made to use a raw material which does not cause the
refractive index difference, it is still difficult to satisfy other
properties required of a flexographic printing plate.
Further, JP-A-5-150451 discloses a water-developable photosensitive resin
composition containing three-dimensionally crosslinked fine particles
produced from a conjugated diene monomer, a hydrophobic elastomer having a
diene-based unit and a hydrophilic polymer. This composition shows the
rubbery resilience which a flexographic printing plate is required to
have, while it is poor in water resistance since a hydrophilic polymer is
contained. Further, it is poor in heat resistance, oxidation resistance
and ozone resistance since a conjugated diene-based material contained,
and it is therefore required to incorporate relatively large amounts of an
antioxidant and an agent for the prevention of deterioration with ozone.
Moreover, a pressure apparatus is required for obtaining crosslinked fine
particles by the polymerization of the diene-based monomer.
On the other hand, the present inventors have found that the following
resin composition for a water-developable flexographic printing plate has
sufficient rubbery resilience and sufficient water resistance, and have
already proposed the same (see JP-A-05-32743). This resin composition
comprises a microgel having core and shell portions bonded to each other
and having a hydrophilic group and a reactive group on its surface,
obtained by copolymerizing an acrylic monomer containing a tertiary amino
group and other acrylic monomer, neutralizing the resultant copolymer with
an acid, adding an epoxy group and an .alpha.,.beta.-ethylenically
unsaturated compound to the neutralized copolymer to prepare a reactive
polymer emulsifying agent, polymerizing a polydiene-based acrylate and/or
a polyurethane-based acrylate in the presence of the reactive polymer
emulsifying agent, and further adding an epoxy group and an
.alpha.,.beta.-ethylenically unsaturated compound to the surface of the
resultant resin fine particles, a diene-based polymer and a photosensitive
monomer. However, the above resin composition is somewhat poor in heat
resistance, oxidation resistance and ozone resistance due to the
diene-based material. Further, there is another defect in that since the
polybutadiene-based acrylate and the polyurethane-based acrylate are
expensive, the flexographic printing plate is expensive.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide a novel reactive
microgel which can be suitably applied to a photosensitive resin
composition for a water-developable flexographic printing plate.
It is another object of the present invention to provide a novel reactive
microgel which can be stably synthesized with a simple apparatus and can
be suitably applied to a photosensitive resin composition for a
water-developable flexographic printing plate.
It is further another object of the present invention to provide a
photosensitive resin composition for a water-developable flexographic
printing plate which has rubbery resilience and is excellent in water
resistance, oxidation resistance and ozone resistance.
According to the present invention, there is provided a reactive microgel
having an average particle diameter of 1 to 10 .mu.m, formed of
microgel particles, as a core, synthesized from an acrylic monomer in an
aqueous medium in the presence of an oil-soluble initiator and in the
presence of a reactive polymer emulsifier which is an adduct of a
neutralized product of an acrylic copolymer having a tertiary amino group
with a compound having an epoxy group and an .alpha.,.beta.-unsaturated
double bond, and a nonionic emulsifier having an HLB of 12 to 16, and
a compound having an epoxy group and an .alpha.,.beta.-unsaturated double
bond, attached to surfaces of the microgel particles.
According to the present invention, there is further provided a
photosensitive resin composition for a water-developable flexographic
printing plate, comprising 30 to 80 parts by weight of the above reactive
microgel (A), 5 to 60 parts by weight of an ethylene-vinyl acetate
copolymer and/or an ethylene-ethyl acrylate copolymer (B), 1 to 60 parts
by weight of a compound having an .alpha.,.beta.-ethylenically unsaturated
double bond (C) and 0.01 to 10 parts by weight of a photopolymerization
initiator (D).
DETAILED DESCRIPTION OF THE INVENTION
The reactive microgel of the present invention will be explained
hereinafter. The reactive microgel of the present invention has an average
particle diameter of 1 to 10 .mu.m, and is formed of
microgel particles, as a core, synthesized from an acrylic monomer in an
aqueous medium in the presence of an oil-soluble initiator and in the
presence of a reactive polymer emulsifier which is an adduct of a
neutralized product of an acrylic copolymer having a tertiary amino group
with a compound having an epoxy group and an .alpha.,.beta.-unsaturated
double bond, and a nonionic emulsifier having an HLB of 12 to 16, and
a compound having an epoxy group and an .alpha.,.beta.-unsaturated double
bond, attached to surfaces of the microgel particles.
The acrylic copolymer having a tertiary amino group is obtained by
copolymerizing a monomer having a tertiary amino group such as
N,N-dimethylaminoethyl (meth)acrylate or N,N-diethylaminoethyl
(meth)acrylate and other acrylic monomer. The "other" acrylic monomer
includes C.sub.1 -C.sub.22 alkyl (meth)acrylates such as methyl
(meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, hexyl
(meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate and
stearyl (meth)acrylate and (meth)acrylates having a hydroxyl group such as
2-hydroxy (meth)acrylate and hydroxypropyl (meth)acrylate.
The acrylic copolymer having a tertiary amino group preferably has a glass
transition temperature (to be referred to as "Tg" hereinafter) of
20.degree. C. or lower to impart the flexographic printing plate with
rubbery resilience and flexibility. Further, the content of a component
from the monomer having a tertiary amino group in the copolymer is
preferably 10 to 50% by weight. When the above content is less than 10% by
weight, the polymer emulsifier has insufficient hydrophilic nature, and
shows insufficient emulsification performance. When the above content
exceeds 50% by weight, the flexographic printing plate shows poor water
resistance.
The acrylic copolymer having a tertiary amino group is neutralized with an
acid such as hydrochloric acid, formic acid, acetic acid, (meth)acrylic
acid or succinic acid, and then a compound having an epoxy group and an
.alpha.,.beta.-unsaturated double bond is attached thereto, so that the
reactive polymer emulsifier is obtained. The compound having an epoxy
group and an .alpha.,.beta.-unsaturated double bond includes glycidyl
acrylate and glycidyl methacrylate.
The nonionic emulsifier having an HLB of 12 to 16 is selected from
polyoxyethylene lauryl available, for example, in the trade of Emulgen 108
or 120, polyoxyethylene cetyl ether available, for example, in the trade
name of Emulgen 220, polyoxyethylene stearyl alcohol available, for
example, in the trade name of Emulgen 320P, polyoxyethylene oleyl ether
available, for example, in the trade name of Emulgen 409P or 420,
polyoxyethylene octylphenyl ether available, for example, in the trade
name of Emulgen 810, polyoxyethylene nonylphenyl ether available, for
example, in the trade name of Emulgene 910 or 911, polyoxyethylene
sorbitane monolaurate available, for example, in the trade name of RHEODOL
TW-S120, polyoxyethylene sorbitol tetraoleate available, for example, in
the trade name of RHEODOL 460, polyethylene glycol monolaurate available,
for example, in the trade name of EMANON 1112 (Emulgen and EMANON are all
trade names of Kao Corp.) and a reactive nonionic emulsifier having an
acryloyl group available, for example, in the trade name of Adecalia soap
NE-10 (supplied by Asahi Denka K.K.).
The oil-soluble initiator includes 2,2'-azobis(2-methylbutyronitrile),
2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile) and
2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile).
The acrylic monomer to form a core includes C.sub.1 -C.sub.22 alkyl
(meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl
(meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl
(meth)acrylate and stearyl (meth)acrylate and (meth)acrylates having a
hydroxyl group such as 2-hydroxy (meth)acrylate and hydroxypropyl
(meth)acrylate.
The above reactive polymer emulsifier, the above nonionic emulsifier having
an HLB of 12 to 16, the above oil-soluble initiator and the above acrylic
monomer to form a core are uniformly mixed, and either the mixture is
stirred with a disper, a homomixer or the like in the presence of an
aqueous medium, or an aqueous medium is added dropwise to the mixture
while the mixture is stirred, to prepare a monomer mixture in the form of
oil drops. Then, the monomer mixture is polymerized under heat under
nitrogen gas current, whereby an aqueous dispersion of a microgel is
obtained. The microgel preferably has a Tg of 20.degree. C. or lower to
obtain a flexographic printing plate having rubbery resilience and
flexibility.
The amount of the reactive polymer emulsifier per 100 parts by weight of
the acrylic monomer to form a core is 1 to 20 parts by weight, preferably
2 to 15 parts by weight. The amount of the nonionic emulsifier per 100
parts by weight of the acrylic monomer to form a core is 0.1 to 15 parts
by weight, preferably 0.5 to 10 parts by weight. When the amount of any
one of the above emulsifiers is smaller than the lower limit of the above
corresponding amount range, the stability of the emulsion is poor, or it
is difficult to impart the microgel particle surface with sufficient
hydrophilic nature. When the above amount is too large, the flexographic
printing plate may show poor water resistance.
The amount of the oil-soluble initiator per 100 parts by weight of the
acrylic monomer to form a core is preferably 0.1 to 5 parts by weight.
When the amount of the oil-soluble initiator is too small, the
polymerization rate does not increase as required, and the acrylic monomer
may remain. When it is too large, the molecular weight of the microgel
does not increase as required, and the flexographic printing plate may be
poor in durability and flexibility.
The microgel is obtained as three-dimensionally crosslinked resin fine
particles when it is synthesized from the above acrylic monomer alone.
However, for imparting a flexographic printing plate with rubbery
resilience, durability and stability of developability with time (i.e.,
for increasing the crosslinking degree of the core), it is preferred to
use a polyfunctional acrylic monomer in combination. The polyfunctional
acrylic monomer is selected from di(meth)acrylates such as ethylene glycol
di(meth)acrylate, hexamethylenediol di(meth)acrylate, neopentyl glycol
di(meth)acrylate and C.sub.14 -C.sub.15 alkylene di(meth)acrylate,
trimethylolpropane triacrylate, pentaerythritol tetraacrylate and glycerin
triacrylate.
The amount of the above poly functional acrylic monomer based on the
acrylic monomer to form a core is preferably 1 to 40% by weight. When the
amount of the polyfunctional acrylic monomer is less than the above lower
limit, the flexographic printing plate is liable to be poor in water
resistance and stability of developability with time. When it is greater
than the above upper limit, the microgel is liable to have too high a
hardness to give a flexographic printing plate having a low hardness and
flexibility.
A compound having an epoxy group and an .alpha.,.beta.-unsaturated double
bond is added to the aqueous dispersion of the microgel obtained above,
and the mixture is heated, whereby an aqueous dispersion of the reactive
microgel of the present invention is obtained. The compound having an
epoxy group and an .alpha.,.beta.-unsaturated double bond includes
glycidyl acrylate and glycidyl methacrylate. The so-obtained aqueous
dispersion of the reactive microgel is dried under heat and/or under
reduced pressure, whereby a microgel powder or microgel flakes are
obtained.
The average particle diameter of the reactive microgel obtained above is
preferably 1 to 10 .mu.m, more preferably 2 to 5 .mu.m, and the reactive
microgel having such an average particle diameter can be used in the
photosensitive resin composition for a flexographic printing plate,
provided by the present invention. When the average particle diameter of
the reactive microgel is smaller than the above lower limit, the
flexographic printing plate is poor in water-developability and stability
of water-developability with time. When the above average particle
diameter is larger than the above upper limit, the resolution of the
flexographic printing plate is adversely affected. The reactive microgel
generally has a refractive index of 1.46 to 1.49.
The photosensitive resin composition for a water-developable flexographic
printing plate, provided by the present invention, will be explained
hereinafter.
The photosensitive resin composition of the present invention contains 30
to 80 parts by weight of the above reactive microgel (A) of the present
invention, 5 to 60 parts by weight of an ethylene-vinyl acetate copolymer
and/or an ethylene-ethyl acrylate copolymer (B), 1 to 60 parts by weight
of a compound having an .alpha.,.beta.-ethylenically unsaturated double
bond (C) and 0.01 to 10 parts by weight of a photopolymerization initiator
(D).
When the amount of the tertiary amino group (A) is smaller than the above
lower limit, the flexographic printing plate is liable to show no
water-developability. When it is larger than the above upper limit, the
flexographic printing plate is liable to be poor in strength and water
resistance.
When the amount of the ethylene-vinyl acetate copolymer and/or the
ethylene-ethyl acrylate copolymer (B) is smaller than the above lower
limit, the flexographic printing plate is liable to be unsatisfactory in
strength and water resistance. When it is larger than the above upper
limit, the flexographic printing plate is liable to be poor in
water-developability.
When the amount of the compound having an .alpha.,.beta.-ethylenically
unsaturated double bond (C) is smaller than the above lower limit, the
flexographic printing plate is liable to be unsatisfactory in water
resistance and physical properties. When it is greater than the above
upper limit, the printing plate has too high a rubber hardness to be used
as a flexographic printing plate.
The ethylene-vinyl acetate copolymer and the ethylene-ethyl acrylate
copolymer (B) can be obtained by copolymerizing ethylene and vinyl acetate
or ethyl acrylate in any amounts, while the ethylene-vinyl acetate
copolymer and the ethylene-ethyl acrylate copolymer (B) preferably have a
refractive index different from that of the reactive microgel of the
present invention by 0.02 or less, and a JIS-A hardness of 60 or less.
When the refractive index of the ethylene-vinyl acetate copolymer and/or
the ethylene-ethyl acrylate copolymer (B) is different from that of the
reactive microgel (h) by more than 0.2, the photosensitive resin
composition is free of transparency, and the resolution required of a
flexographic printing plate cannot be obtained. When the above JIS-A
hardness exceeds 60, the photosensitive resin composition has a high
hardness, and the use thereof for a flexographic printing plate is
limited.
The compound having an .alpha.,.beta.-ethylenically unsaturated double bond
(C) serves to impart the photosensitive resin composition with
photo-curability. The photosensitive resin composition containing the
compound having an .alpha.,.beta.-ethylenically unsaturated double bond in
combination with the photopolymerization initiator cures itself after
being exposed to light, and gives a resolution required as a flexographic
printing plate when developed with water. The compound having an
.alpha.,.beta.-ethylenically unsaturated double bond (C) is not specially
limited if it is compatible with the ethylene-vinyl acetate copolymer and
the ethylene-ethyl acrylate copolymer (B) before and after the
photosensitive resin composition is cured, or if it has almost no
different refractive index from that of the above copolymer(s) (B).
The compound having an .alpha.,.beta.-ethylenically unsaturated double bond
(C) is selected from monofunctional monomers and polyfunctional monomers.
The monofunctional monomers include C.sub.1 -C.sub.22 alkyl
(meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl
(meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl
(meth)acrylate and stearyl (meth)acrylate, (meth)acrylates having a
hydroxyl group such as 2-hydroxy (meth)acrylate and hydroxypropyl
(meth)acrylate, norbornyl (meth)acrylate, vinylpyrrolidone, vinylaniline
and acrylamide.
The polyfunctional monomers include ethylene glycol di(meth)acrylate,
hexamethylenediol di(meth)acrylate, neopentyl glycol di(meth)acrylate,
C.sub.14 -C.sub.15 alkylene di(meth)acrylate, trimethylolpropane
triacrylate, pentaerythritol tetraacrylate and glycerin triacrylate,
polyester acrylate, polyurethane acrylate and polyol acrylate.
The polyfunctional monomer is preferred since it is excellent in
photo-curability. The above polyfunctional monomers may be used alone or
in combination. Further, the polyfunctional monomer may be used in
combination with the monofunctional monomer.
The photopolymerization initiator (D) is not specially limited if it reacts
when exposed to ultraviolet light or the like and cures the above
monomers. The photopolymerization initiator (D) includes benzoin ethers,
benzophenones, xanthones and acetophenones. These initiators may be used
alone or in combination. Further, the photopolymerization initiator (D)
may be used In combination with a photo-initiator auxiliary selected from
amines.
The photosensitive resin composition for a water-developable flexographic
printing plate, provided by the present invention, may further contain an
organic or inorganic filler, a heat polymerization inhibitor, an
antioxidant, a preventer for deterioration with ozone, a dye and a flow
regulator.
The photosensitive resin composition of the present invention is kneaded
with a kneading apparatus such as a two-roll mill, a Banbury mixer, a
kneader or an extruder, and formed into a laminate of a substrate film,
the photosensitive resin composition and a cover film to obtain a
water-developable flexographic printing plate. The so-obtained
water-developable flexographic printing plate is exposed to light through
the substrate film, the cover film is removed, and a negative film is
intimately attached. The resultant printing plate is exposed to light in
an appropriate dose, developed by brush-washing an unexposed portion with
water or hot water, dried and post-exposed to obtain a flexographic
printing plate.
EXAMPLES
The present invention will be detailed hereinafter with reference to
Examples, in which "part" stands for "part by weight".
Example 1
A two-liter flask was charged with 195 parts of N,N-dimethylaminoethyl
methacrylate, 455 parts of n-lauryl methacrylate and 350 parts of
isopropanol, and while the mixture was stirred under nitrogen current, the
mixture was temperature-increased to 75.degree. C. Then, 6.5 parts of
azobisisobutyronitrile was added, and the mixture was heated at 80.degree.
C. for 5 hours to give a polymer solution. The polymer solution was
allowed to stand overnight at room temperature, and 75 parts of acetic
acid and 50 parts of glycidyl methacrylate were added. While the mixture
was stirred under air current, the mixture was heated at 50.degree. C. for
5 hours to give a reactive polymer emulsifier solution.
A two-liter flask was charged with 50 parts of the above-obtained reactive
polymer emulsifier, 15 parts of a nonionic emulsifier ("Emulgen 420", HLB
13.6, supplied by Kao Corp.), 270 parts of 2-ethylhexyl acrylate, 30 parts
of hexamethylene glycol diacrylate and 2 parts of azobisisobutyronitrile,
and while the mixture was moderately stirred at room temperature, 600
parts of ion-exchanged water was dropwise added over 1 hour. Then, under
nitrogen current, the mixture was temperature-increased to 80.degree. C.
and maintained at this temperature for 3 hours to give an aqueous
dispersion of a microgel. The aqueous dispersion of a microgel was allowed
to stand overnight at room temperature, and then 20 parts of glycidyl
methacrylate was added. The mixture was heated at 50.degree. C. for 3
hours to give an aqueous dispersion of a reactive microgel. The aqueous
dispersion of a reactive microgel was measured for an average particle
diameter by a light scattering method to show 3 .mu.m. The aqueous
dispersion also showed a refractive index of 1.47. The aqueous dispersion
of a reactive microgel was freeze-dried to give a white powder.
60 Parts of the above-obtained reactive microgel powder, 30 parts of an
ethylene-vinyl acetate copolymer ("Evaflex EV40X", JIS-A hardness 43,
refractive index 1.48, supplied by Du Pont-Mitsui Polychemicals Co.,
Ltd.), 10 parts of hexamethylene glycol diacrylate, 0.5 part of a
photopolymerization initiator ("Darocure 1173", supplied by Merck) and 0.1
part of hydroquinone were kneaded with a double-armed kneader at room
temperature for 20 minutes. Then, the resultant composition was sandwiched
with polyester films and pressed to give a raw flexographic printing plate
having a thickness of 1.5 mm. One surface of the raw flexographic printing
plate was exposed to a 15 W ultraviolet light lamp for 10 seconds, and
then, the polyester film forming the other surface was removed. A negative
film was intimately attached to the revealed surface, and the surface was
exposed to the 15 W ultraviolet light lamp for 3 minutes. The raw
flexographic printing plate was developed by brush-washing it with water
for 10 minutes, dried at 60.degree. C. for 15 minutes, and post-exposed to
the 15 W ultraviolet light lamp for 10 minutes to give a flexographic
printing plate. The so-obtained flexographic printing plate had a JIS-A
hardness of 50, and it showed a thickness change of 1.8% after tested for
water resistance by immersing it in ion-exchanged water for 1 day.
Concerning the transparency, the raw flexographic printing plate had a
haze value of 30, and the cured flexographic printing plate had a haze
value of 35. The raw flexographic printing plate showed almost no change
in water-developability after being allowed to stand at 50.degree. C. for
2 months and after being allowed to stand at 120.degree. C. for 2 hours.
Example 2
50 Parts of the same reactive microgel powder as that obtained in Example
1, 30 parts of an ethylene-vinyl acetate copolymer ("Evaflex EV45LX",
JIS-A hardness 34, refractive index 1.47, supplied by Du Pont-Mitsui
Polychemicals Co., Ltd.), 15 parts of C.sub.14 -C.sub.15 alkyl diacrylate
("SR2000A", supplied by Kayaku Sartomer K.K.) and 0.1 part of a
photopolymerization initiator ("Irgacure 651", supplied by Ciba Geigy)
were kneaded with a two-roll mill for 10 minutes. Then, the resultant
composition was processed in the same manner as in Example 1 to give a raw
flexographic printing plate having a thickness of 1.5 mm. The raw
flexographic printing plate was exposed, developed and post-exposed in the
same manner as in Example 1 to give a flexographic printing plate. The
so-obtained flexographic printing plate had a JIS-A hardness of 45, and it
showed a thickness change of 1.9% after tested for water resistance by
immersing it in ion-exchanged water for 1 day. Concerning the
transparency, the raw flexographic printing plate had a haze value of 36,
and the cured flexographic printing plate had a haze value of 40. The raw
flexographic printing plate showed almost no change in
water-developability after being allowed to stand at 50.degree. C. for 2
months, and after being allowed to stand at 120.degree. C. for 2 hours.
Example 3
50 Parts of the same reactive microgel powder as that obtained in Example
1, 35 parts of an ethylene-ethyl acrylate copolymer ("Evaflex EEA A-709",
JIS-A hardness 49, refractive index 1.47, supplied by Du Pont-Mitsui
Polychemicals Co., Ltd.), 15 parts of C.sub.14 -C.sub.15 alkyl diacrylate
("SR2000A", supplied by Kayaku Sartomer K.K.) and 0.1 part of a
photopolymerization initiator ("Irgacure 651", supplied by Ciba
Geigy.).were kneaded with a two-roll mill for 10 minutes. Then, the
resultant composition was processed in the same manner as in Example 1 to
give a raw flexographic printing plate having a thickness of 1.5 mm. The
raw flexographic printing plate was exposed, developed and post-exposed in
the same manner as in Example 1 to give a flexographic printing plate. The
so-obtained flexographic printing plate had a JIS-A hardness of 48, and it
showed a thickness change of 1.7% after tested for water resistance by
immersing it in ion-exchanged water for 1 day. Concerning the
transparency, the raw flexographic printing plate had a haze value of 34,
and the cured flexographic printing plate had a haze value of 30. The raw
flexographic printing plate showed almost no change in
water-developability after being allowed to stand at 50.degree. C. for 2
months, and after being allowed to stand at 120.degree. C. for 2 hours.
Example 4
A two-liter flask was charged with 195 parts of N,N-diethylaminoethyl
methacrylate, 455 parts of 2-ethylhexyl methacrylate and 350 parts of
isopropanol, and while the mixture was stirred under nitrogen current, the
mixture was temperature-increased to 75.degree. C. Then, 6.5 parts of
azobisisobutyronitrile was added, and the mixture was heated at 80.degree.
C. for 5 hours to give a polymer solution. The polymer solution was
allowed to stand overnight at room temperature, and 60 parts of acetic
acid and 50 parts of glycidyl methacrylate were added. While the mixture
was stirred under air current, the mixture was heated at 50.degree. C. for
5 hours to give a reactive polymer emulsifier solution.
A two-liter flask was charged with 50 parts of the above-obtained reactive
polymer emulsifier, 10 parts of a nonionic emulsifier ("Emulgen 120", HLB
15.3, supplied by Kao Corp.), 270 parts of 2-ethylhexyl acrylate, 40 parts
of C.sub.14 -C.sub.15 alkyl diacrylate and 2 parts of
azobisisobutyronitrile, and while the mixture was moderately stirred at
room temperature, 600 parts of ion-exchanged water was dropwise added over
1 hour. Then, under nitrogen current, the mixture was
temperature-increased to 65.degree. C. and maintained at this temperature
for 3 hours to give an aqueous dispersion of a microgel. The aqueous
dispersion of a microgel was allowed to stand overnight at room
temperature, and then 20 parts of glycidyl methacrylate was added. The
mixture was heated at 50.degree. C. for 3 hours to give an aqueous
dispersion of a reactive microgel. The aqueous dispersion of a reactive
microgel was measured for an average particle diameter by a light
scattering method to show 3 .mu.m. The aqueous dispersion also showed a
refractive index of 1.47. The aqueous dispersion of a reactive microgel
was freeze-dried to give a white powder.
50 Parts of the above-obtained reactive microgel powder, 40 parts of an
ethylene-vinyl acetate copolymer ("Evaflex EV40X", JIS-A hardness 43,
refractive index 1.48, supplied by Du Pont-Mitsui Polychemicals Co.,
Ltd.), 5 parts of dipentaerythritol hexaacrylate, 5 parts of isophorone
acrylate, 0.5 part of a photopolymerization initiator ("Darocure 1173",
supplied by Merck) and 0.1 part of hydroquinone were kneaded with a
twin-screw kneader at 100.degree. C. for 5 minutes. Then, the resultant
composition was processed in the same manner as in Example 1 to give a raw
flexographic printing plate having a thickness of 1.5 mm. The raw
flexographic printing plate was exposed, developed and post-exposed in the
same manner as in Example 1 to give a flexographic printing plate. The
so-obtained flexographic printing plate had a JIS-A hardness of 45, and it
showed a thickness change of 2.0% after tested for water resistance by
immersing it in ion-exchanged water for 1 day. Concerning the
transparency, the raw flexographic printing plate had a haze value of 35,
and the cured flexographic printing plate had a haze value of 35. The raw
flexographic printing plate showed almost no change in
water-developability after being allowed to stand at 50.degree. C. for 2
months, and after being allowed to stand at 120.degree. C. for 2 hours.
Example 1
60 Parts of the same reactive microgel powder as that obtained in Example
1, 30 parts of an ethylene-vinyl acetate copolymer ("Evaflex EV450", JIS-A
hardness 90, refractive index 1.49, supplied by Du Pont-Mitsui
Polychemicals Co., Ltd.), 10 parts of hexamethylene glycol diacrylate, 0.5
part of a photopolymerization initiator ("Darocure 1173", supplied by
Merck) and 0.1 part of hydroquinone were kneaded with a double-armed
kneader at room temperature for 20 minutes. Then, the resultant
composition was processed in the same manner as in Example 1 to give a raw
flexographic printing plate having a thickness of 1.5 mm. The raw
flexographic printing plate was exposed, developed and post-exposed in the
same manner as in Example 1 to give a flexographic printing plate. The
so-obtained flexographic printing plate had a JIS-A hardness of 75, and it
showed a thickness change of 1.7% after being tested for water resistance
by immersing it in ion-exchanged water for 1 day. Concerning the
transparency, the raw flexographic printing plate had a haze value of 60,
and the cured flexographic printing plate had a haze value of 57. The raw
flexographic printing plate showed almost no change in
water-developability after being allowed to stand at 50.degree. C. for 2
months, and after being allowed to stand at 120.degree. C. for 2 hours.
Comparative Example 1
A 2-liter flask was charged with 15 parts of a nonionic emulsifier
("Emulgen 420", HLB 13.6), 270 parts of 2-ethylhexyl acrylate, 30 parts of
hexamethylene glycol diacrylate and 2 parts of azobisisobutyronitrile, and
while the mixture was stirred at room temperature, 600 parts of
ion-exchanged water was dropwise added over 1 hour. Then, the mixture was
temperature-increased to 80.degree. C. under nitrogen current to carry out
the polymerization, while the polymerization was not carried out stably
and the mixture was gelled.
Comparative Example 2
A two-liter flask was charged with 50 parts of the same reactive polymer
emulsifier as that obtained in Example 1, 15 parts of a nonionic
emulsifier ("Emulgen 950", HLB 18.2, supplied by Kao Corp.), 270 parts of
2-ethylhexyl acrylate, 30 parts of hexamethylene glycol diacrylate and 2
parts of azobisisobutyronitrile, and while the mixture was moderately
stirred at room temperature, 600 parts of ion-exchanged water was dropwise
added over 1 hour. Then, the mixture was temperature-increased to
80.degree. C. under nitrogen current to carry out the polymerization,
while the polymerization was not carried out stably and the mixture was
gelled.
Comparative Example 3
A two-liter flask was charged with 270 parts of 2-ethylhexyl acrylate, 30
parts of hexamethylene glycol diacrylate, 10 parts of sodium
dodecylbenzenesulfonate, 15 parts of a nonionic emulsifier ("Emulgen 420",
HLB 13.6, supplied by Kao Corp.) and 600 parts of ion-exchanged water, and
while the mixture was stirred, the mixture was temperature-increased to
65.degree. C. under nitrogen current. Further, 20 parts of a 5% ammonium
persulfate aqueous solution and 20 parts of a 5% sodium thiosulfate
aqueous solution both of which were water-soluble polymerization
initiators were added, and the mixture was heated at 70.degree. C. for 5
hours to give an aqueous dispersion of a microgel having an average
particle diameter, measured by a light scattering method, of 0.2 .mu.m and
a refractive index of 1.47. The so-obtained aqueous dispersion of a
microgel was freeze-dried to give a white powder.
60 Parts of the above-obtained reactive microgel powder, 30 parts of an
ethylene-vinyl acetate copolymer ("Evaflex EV40X", JIS-A hardness 43,
refractive index 1.48, supplied by Du Pont-Mitsui Polychemicals Co.,
Ltd.), 10 parts of hexamethylene glycol diacrylate, 0.5 part of a
photopolymerization initiator ("Darocure 1173", supplied by Merck) and 0.1
part of hydroquinone were kneaded with a double-armed kneader at room
temperature for 20 minutes. Then, the kneaded mixture was processed in the
same manner as in Example 1 to give a raw flexographic printing plate
having a thickness of 1.5 mm. This raw flexographic printing plate showed
no developability with water at 50.degree. C. when it was in a non-exposed
state.
Comparative Example 4
A two-liter flask was charged with 130 parts of methacrylic acid, 520 parts
of n-lauryl methacrylate and 350 parts of isopropanol, and the mixture was
temperature-increased to 75.degree. C. with stirring under nitrogen
current. Then, 6.5 parts of azobisisobutyronitrile was added, and the
mixture was heated at 80.degree. C. for 5 hours to give a polymer
solution. This polymer solution was allowed to stand overnight at room
temperature, and 600 parts of a 10% sodium hydroxide aqueous solution was
added to give a polymer emulsifier solution.
A two-liter flask was charged with 80 parts of the above-obtained polymer
emulsifier, 15 parts of a nonionic emulsifier ("Emulgen 420", HLB 13.6,
supplied by Kao Corp.), 270 parts of 2-ethylhexyl acrylate, 30 parts of
hexamethylene glycol diacrylate and 2 parts of azobisisobutyronitrile, and
while the mixture was moderately stirred under nitrogen current, 600 parts
of ion-exchanged water was added over 1 hour. Then, under nitrogen
current, the mixture was temperature-increased to 80.degree. C. and this
temperature was maintained for 3 hours to give an aqueous dispersion of a
microgel. The aqueous dispersion of a reactive microgel was measured for
an average particle diameter by a light scattering method to show 3 .mu.m.
The aqueous dispersion also showed a refractive index of 1.47. The aqueous
dispersion of a reactive microgel was freeze-dried to give a white powder.
60 Parts of the above-obtained microgel powder, 30 parts of an
ethylene-vinyl acetate copolymer ("Evaflex EV40X", JIS-A hardness 43,
refractive index 1.48, supplied by Du Pont-Mitsui Polychemicals Co.,
Ltd.), 10 parts of hexamethylene glycol diacrylate, 0.5 part of a
photopolymerization initiator ("Darocure 1173", supplied by Merck) and 0.1
part of hydroquinone were kneaded with a double-armed kneader at room
temperature for 20 minutes. Then, the resultant composition was processed
in the same manner as in Example 1 to give a raw flexographic printing
plate having a thickness of 1.5 mm. The raw flexographic printing plate
was exposed, developed and post-exposed in the same manner as in Example 1
to give a flexographic printing plate. The so-obtained flexographic
printing plate had a JIS-A hardness of 50, while it showed a thickness
change of 8.0% after being tested for water resistance by immersing it in
ion-exchanged water for 1 day. The immersed flexographic printing plate
was considerably fragile.
Comparative Example 5
A two-liter flask was charged with 50 parts of the same reactive polymer
emulsifier as that obtained in Example 1, 15 parts of a nonionic
emulsifier ("Emulgen 420", HLB 13.6, supplied by Kao Corp.), 270 parts of
2-ethylhexyl acrylate, 30 parts of hexamethylene glycol diacrylate and 2
parts of azobisisobutyronitrile, and while the mixture was vigorously
stirred at room temperature, 600 parts of ion-exchanged water was dropwise
added over 1 hour. Then, the mixture was stirred with a homomixer for 60
minutes. Under nitrogen current, the mixture was temperature-increased to
80.degree. V., and this temperature was maintained for 3 hours to give an
aqueous dispersion of a microgel. The so-obtained aqueous dispersion of a
microgel was allowed to stand overnight at room temperature. Then, 20
parts of glycidyl methacrylate was added, and the mixture was heated at
50.degree. C. for 3 hours to give an aqueous dispersion of a reactive
microgel. The aqueous dispersion of a reactive microgel was measured for
an average particle diameter by a light scattering method to show 0.4
.mu.m. The aqueous dispersion also showed a refractive index of 1.47. The
aqueous dispersion of a reactive microgel was freeze-dried to give a white
powder.
60 Parts of the above-obtained reactive microgel powder, 30 parts of an
ethylene-vinyl acetate copolymer ("Evaflex EV40X", JIS-A hardness 43,
refractive index 1.48, supplied by Du Pont-Mitsui Polychemicals Co.,
Ltd.), 10 parts of hexamethylene glycol diacrylate, 0.5 part of a
photopolymerization initiator ("Darocure 1173", supplied by Merck) and 0.1
part of hydroquinone were kneaded with a double-armed kneader at room
temperature for 20 minutes. Then, the resultant composition was processed
in the same manner as in Example 1 to give a raw flexographic printing
plate having a thickness of 1.5 mm. The raw flexographic printing plate
was exposed, developed and post-exposed in the same manner as in Example 1
to give a flexographic printing plate. The so-obtained flexographic
printing plate had a JIS-A hardness of 50, and it showed a thickness
change of 1.8% after tested for water resistance by immersing it in
ion-exchanged water for 1 day. Concerning the transparency, the raw
flexographic printing plate had a haze value of 30, and the cured
flexographic printing plate had a haze value of 35. However, the raw
flexographic printing plate showed no developability with water after
being allowed to stand at 50.degree. C. for 3 days.
Comparative Example 6
50 Parts of the same reactive microgel powder as that obtained in Example
1, 35 parts of an ethylene-propylene rubber ("JSREP11", refractive index
1.47, supplied by Japan Synthetic Rubber), 15 parts of C.sub.14 -C.sub.15
alkyl diacrylate ("SR2000A", supplied by Kayaku Sartomer K.K.) and 0.1
part of a photopolymerization initiator ("Irgacure 651", supplied by Ciba
Geigy) were kneaded with a two-roll mill for 10 minutes. Then, the
resultant composition was processed in the same manner as in Example 1 to
give a raw flexographic printing plate having a thickness of 1.5 mm. This
raw flexographic printing plate had a haze value of 30 or had excellent
transparency. However, when the flexographic printing plate was exposed to
a 15 W ultraviolet light lamp for 20 minutes, it was free of flexibility
and not suitable for the use thereof as a flexographic printing plate.
Comparative Example 7
50 Parts of the same reactive microgel powder as that obtained in Example
1, 35 parts of an acrylic rubber ("AR72HF", refractive index 1.47,
supplied by Nippon Zeon Co., Ltd.), 15 parts of C.sub.14 -C.sub.15 alkyl
diacrylate ("SR2000A", supplied by Kayaku Sartomer K.K.) and 0.1 part of a
photopolymerization initiator ("Irgacure 651", supplied by Ciba Geigy)
were kneaded with a two-roll mill for 10 minutes. Then, the resultant
composition as processed in the same manner as in Example 1 to give a raw
flexographic printing plate having a thickness of 1.5 mm. This raw
flexographic printing plate had a haze value of 30 or had excellent
transparency. However, when the flexographic printing plate was cured by
exposing it to a 15 W ultraviolet light lamp for 20 minutes and immersed
in water for 25 hours, it showed a thickness change of over 8, and was not
suitable for the use thereof as a flexographic printing plate.
Comparative Example 8
50 Parts of the same reactive microgel powder as that obtained in Example
1, 35 parts of a butadiene rubber ("JSRBR02LL", refractive index 1.51,
supplied by Japan Synthetic Rubber), 15 parts of C.sub.14 -C.sub.15 alkyl
diacrylate ("SR2000A", supplied by Kayaku Sartomer K.K.) and 0.1 part of a
photopolymerization initiator ("Irgacure 651", supplied by Ciba Geigy)
were kneaded with a two-roll mill for 10 minutes. Then, the resultant
composition was processed in the same manner as in Example 1 to give a raw
flexographic printing plate having a thickness of 1.5 mm. This raw
flexographic printing plate had a haze value of 96 or had no transparency,
and no resolution was achieved.
As explained above, according to the present invention, a resin composition
for a water- or hot water-developable photosensitive flexographic printing
plate excellent in water resistance, flexibility, heat resistance,
oxidation resistance and ozone resistance and a reactive microgel suitable
for use therefor can be produced stably at a low cost.
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